Continuous medium theory for nonequilibrium solvation : II. Interaction energy between solute charge and reaction field and single-sphere model for spectral shift
Copyright 2004 Wiley Periodicals, Inc. J Comput Chem 25: 835-842, 2004
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 25(2004), 6 vom: 30. Apr., Seite 835-42 |
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| Weitere Verfasser: | , , |
| Format: | Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2004
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article |
| Zusammenfassung: | Copyright 2004 Wiley Periodicals, Inc. J Comput Chem 25: 835-842, 2004 On the basis of continuous medium theory, a model for evaluation of spectral shifts in solution has been developed in this work. The interaction energy between solute dipole and reaction field and the self-energy of the reaction field have been formulated through derivations. Applying the interaction energy expression together with the point dipole approximation to the case of spherical cavity produces new formulations of spectral shifts. The same expression of electrostatic free energy of the nonequilibrium state is achieved by integrating the change of the electrostatic free energy for a charging process. Moreover, generalized formulations evaluating spectral shifts have been established in the charge-potential notation, and the reduction of them to the point dipole case consistently leads to the same formulations of spectral shifts as those by interaction energy approach. Mutual supports provide convincing evidences for the reliability of the present results. In this work, attentions are particularly paid to the conclusion of zero self-energy of the reaction field, which is different from the previous theory. Reasoning and arguments are given on this point. From the present derivations, it is concluded that the spectral shifts of light absorption and emission were theoretically exaggerated in the past, in particular, by a factor of 2 for the spectral shift sum |
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| Beschreibung: | Date Completed 27.05.2004 Date Revised 10.03.2004 published: Print Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |